Dual-cure formulations with components containing uretdione groups

ABSTRACT

The present invention relates to novel formulations which are thermally curable and curable by actinic radiation, known as dual-cure formulations. The present invention also relates to the use, for the production of pigmented and pigment-free coating materials, or else for adhesives and sealants, of the novel formulations that are curable thermally and curable by actinic radiation.

The present invention relates to novel formulations which are thermallycurable and curable by actinic radiation, known as dual-cureformulations. The present invention also relates to the use, for theproduction of pigmented and pigment-free coating materials, or else foradhesives and sealants, of the novel formulations that are curablethermally and curable by actinic radiation.

Formulations curable by actinic radiation are known.

Ethylenically unsaturated prepolymers are described by way of example inP. K. T. Oldring (Ed.), “Chemistry and Technology of UV- andEB-Formulations for Coatings, Inks and Paints”, Vol. II. SITATechnology, London 1991, examples being those based on epoxy acrylates(pages 31 to 68), on urethane acrylates (pages 73 to 123) and onmelamine acrylates (pages 208 to 214). Formulations of this type arealso often mentioned in the patent literature, and examples that may bementioned are JP 62110779 and EP 947 565.

The coating of metallic substrates is a particular problem forradiation-curable formulations, since shrinkage processes can often leadto loss of adhesion. Adhesion promoters comprising phosphoric acid aretherefore often used for these substrates. Examples of this are U.S.Pat. No. 5,128,387 (coating of beer cans) and JP 2001172554 (coating ofvarious cans).

It is known that epoxy acrylates exhibit excellent adhesion and alsoprovide good corrosion prevention on metal substrates. However, adisadvantage of these coatings is low formability after hardening. Forsome coating technologies, e.g. coil coating, the formability of thecoated workpieces without cracking of the coating is of criticalimportance. The aromatic content of these coatings moreover makes themsusceptible to yellowing.

WO 03/022945 describes low-viscosity radiation-curable formulations formetal substrates, based on radiation-curable resins, on monofunctionalreactive diluents and on acidic adhesion promoters. The resins used hereare conventional marketed products obtainable from various suppliers.

EP 902 040, too, relates to radiation-curable formulations. It describesurethane (meth)acrylates with monofunctional esters of an unsaturatedcarboxylic acid, these having been esterified with alcohols, where thesecontain a carbocycle or a heterocycle.

However, many of the systems known from the prior art exhibitdisadvantages, and in particular the hardening of three-dimensionalsubstrates in the shadow zone is difficult or impossible to achieve.

For some time, dual-cure systems have therefore been propagated whichalso include other curing methods alongside radiation-curing. Examplesare WO2001/46286, WO200146285, WO2001/42329, WO2001/23453, WO2000/39183,EP1138710, EP1103572, EP1085065, EP928800. In these, the reaction ofisocyanate-functionalized binder constituents with hydroxy-functionalcomponents is described, leading to additional crosslinking.

If free isocyanates are used here, as for example in WO2001/46286, theresult is a 2-component formulation with restricted pot life.

If, in contrast, externally blocked isocyanates are used (e.g.WO2001/23453), blocking agent is released into the environment duringthe hardening reaction, and this is undesirable for environmentalreasons.

WO 03/016376 describes the use of internally blocked isocyanates(uretdiones) in dual-cure systems. The use of uretdione-containingcomponents there leads to improved intermediate adhesion, but in theexamples listed it has no effect on the hardness and scratch resistanceof the coating (Examples 3, 4 and V2). There is no example giving theperformance of the coating solely with thermal hardening, withoutradiation curing (i.e. simulating the shadow regions).

It is an object of the present invention to develop formulations curableby actinic radiation and curable thermally, which after thermalhardening either with or without prior radiation curing give an adhesivebond or a seal which complies with minimum requirements, i.e. isnon-tack, flexible and chemicals-resistant. This formulation is moreoverintended to be free of blocking agents, for environmental reasons, andto be hardenable below 160° C., so that it can also be used forheat-sensitive substrates.

Surprisingly, it has been found that the formulations according to theinvention achieve the object.

The present invention provides thermally curable and radiation-curableformulations composed of

-   A) from 5 to 90% by weight of at least one radiation-curable    component, which can also contain OH groups,-   B) from 10 to 90% by weight of at least one component containing    uretdione groups, which can also contain OH groups and/or    radiation-curable groups,-   C) from 0.1 to 5% by weight of at least one tetralkylammonium salt    and/or phosphonium salt with halogens, hydroxides, alcoholates or    organic or inorganic acid anions, as counter-ion,    and    from 0.1 to 5% by weight of at least one co-catalyst, selected from-   C1) at least one epoxide    and/or-   C2) at least one metal acetylacetonate.

These materials can moreover also comprise at least one of the followingcomponents, alone or in a mixture:

-   D) from 0.1 to 10% by weight of at least one adhesion promoter,-   E) from 0.2 to 10% by weight of at least one photoinitiator,-   F) from 0.1 to 10% by weight of at least one acid,-   G) from 1 to 40% by weight of monomers and/or polymers and/or    oligomers containing hydroxy groups,-   H) from 0.01 to 50% by weight of at least one pigment and/or other    additives,-   I) from 1 to 70% by weight of at least one solvent.

The thermally curable and radiation-curable formulations according tothe invention have the advantage that when hardened correctly by actinicradiation and thermal energy they retain their full properties withregard to freedom from tack, flexibility and chemicals resistance, butthat they also comply with minimum requirements when hardened purelythermally. These minimum requirements are freedom from tack, chemicalsresistance of at least 20 cycles and Erichsen indentation of at least 7mm.

The radiation-curable resins of component A) are an essential componentof the formulations according to the invention. These involve systemsknown to the person skilled in the art. The production ofradiation-curable resins, oligomers and/or polymers is described by wayof example in “Radiation Curing in Polymer Science & Technology, Vol I:Fundamentals and Methods” by J. P. Fouassier, J. F. Rabek, ElsevierApplied Science, London and New York, 1993, Chapter 5, pages 226 to 236,in “Lackharze”, D. Stoye, W. Freitag, Hanser-Verlag, Vienna, 1996, page85, 94-98, 169 and 265 and in EP 947 565.

As a function of the parent raw material, the resins of component A) canby way of example be epoxy acrylates, polyester acrylates, polyetheracrylates, polyacrylate acrylates, and urethane acrylates and/orpolyester urethane acrylates, alone or in a mixture. The urethaneacrylates can by way of example be based on polyesters or else onpolyethers. The corresponding methacrylates are also known. Otherpolymerizable groups are epoxides and vinyl ethers. These, too, can havebeen linked to various parent resins. An amount of from 1 to 500 mgKOH/g of OH groups can also be present.

Liquid radiation-curable components, known as reactive diluents, canalso be used for A).

Radiation-curable reactive diluents A) and their production aredescribed by way of example in “Radiation Curing in Polymer Science &Technology, Vol I: Fundamentals and Methods” by J. P. Fouassier, J. F.Rabek, Elsevier Applied Science, London and New York, 1993, Chapter 5,pages 237 to 240. These generally involve substances containingmethacrylate or acrylate which are liquid at room temperature andtherefore are capable of lowering the overall viscosity of theformulation. Examples of these products are in particular isobornylacrylate, hydroxypropyl methacrylate, trimethylolpropane monoformalacrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate,trimethylenepropane triacrylate, dipropylene glycol diacrylate,tripropylene glycol diacrylate, hexanediol diacrylate, pentaerythritoltetraacrylate, lauryl acrylate, or else propoxylated or ethoxylatedvariants of these reactive diluents and/or urethanized reactivediluents, such as EBECRYL 1039 (Cytec), and others. It is also possibleto use other liquid components capable of reacting under conditions offree-radical polymerization with, for example, vinyl ether or allylether.

The amount of A) in the formulation varies from 5 to 90% by weight,preferably from 10 to 50% by weight, based on the entire formulation.Particular preference is given to polyester urethane acrylates. Examplesof these are VESTICOAT EP 110 IBOA (product marketed by Evonik DegussaGmbH, Germany, Coatings & Colorants, Difunctional Polyester UrethaneAcrylate) and EBECRYL 1256 (product marketed by Cytec). Particularpreference is also given to monofunctional reactive diluents, inparticular isobornyl acrylate and/or trimethylolpropane monoformalacrylate.

Polyisocyanates containing uretdione groups are well known and aredescribed by way of example in U.S. Pat. No. 4,476,054, U.S. Pat. No.4,912,210, U.S. Pat. No. 4,929,724, and also EP 0 417 603. Acomprehensive overview of industrially relevant processes for thedimerization of isocyanates to uretdiones is provided by J. Prakt. Chem.336 (1994) 185-200. The reaction of isocyanates to give uretdionesgenerally takes place in the presence of soluble dimerization catalyst,e.g. dialkylaminopyridines, trialkylphosphines, phosphorous triamides,triazole derivatives or imidazoles. The reaction—optionally carried outin solvents, but preferably in the absence of solvents—is terminated onreaching a desired conversion, by addition of catalyst poisons. Excessmonomeric isocyanate is then removed by short-path evaporation. If thecatalyst is sufficiently volatile, the reaction mixture can be freedfrom the catalyst during the course of monomer removal. In this case, itis possible to omit addition of catalyst poisons. A wide range ofisocyanates is in principle suitable for the production ofpolyisocyanates containing uretdione groups. According to the invention,preference is given to use of isophorone diisocyanate (IPDI),hexamethylene diisocyanate (HDI), diisocyanatodicyclohexylmethane(H₁₂MDI), 2-methylpentane diisocyanate (MPDI),2,2,4-trimethylhexamethylene diisocyanate/2,4,4-trimethylhexamethylenediisocyanate (TMDI), norbornane diisocyanate (NBDI), methylenediphenyldiisocyanate (MDI), toluidine diisocyanate (TDI) and tetramethylxylylenediisocyanate (TMXDI). Very particular preference is given to IPDI, HDIand H₁₂MDI.

The reaction of these polyisocyanates bearing uretdione groups to givecomponent B) having uretdione groups includes the reaction of the freeNCO groups with polymers or monomers containing hydroxy groups, e.g.polyesters, polythioethers, polyethers, polycaprolactams, polyepoxides,polyesteramides, polyurethanes or low-molecular-weight di-, tri- and/ortetraalcohols as chain extenders and, if appropriate, monoamines and/ormonoalcohols as chain terminators, and has been frequently described (EP0 669 353, EP 0 669 354, DE 30 30 572, EP 0 639 598 or EP 0 803 524).Preference is given to polyesters and monomeric dialcohols. Preferredcomponents B) (hardeners) having uretdione groups have less than 5% byweight of free NCO content and from 1 to 25% by weight of uretdionegroup content (calculated as C₂N₂O₂, molecular weight 84). Component B)having uretdione groups can also have, as well as the uretdione groups,isocyanurate structures, biuret structures, allophanate structures,urethane structures and/or urea structures. Commercially availableexamples of these components B) (hardeners) containing uretdione groupsare VESTAGON BF 1320, VESTAGON, BF 1540 and VESTAGON BF 9030 from EvonikDegussa GmbH.

Component B) having uretdione groups can also contain OH groups and/orradiation-curable groups. If isocyanates containing uretdione groups arereacted with an excess of diols, the result is products containinguretdione groups and containing OH groups. If, in contrast, substancesare used in the same reaction which bear not only groups reactivetowards isocyanates but also functionalities capable of free-radicalpolymerization (e.g. hydroxyethyl acrylate), the result is a productcontaining uretdione groups and having additional radiation-curablegroups.

The proportion of component B) containing uretdione groups can be from10 to 90% by weight, preferably from 20 to 50% by weight, based on theentire formulation. Catalysts used for C) are tetralkylammonium saltsand/or phosphonium salts with halogens, with hydroxides, withalcoholates or with organic or inorganic acid anions as counter-ion.Examples of these are:

tetramethylammonium formate, tetramethylammonium acetate,tetramethylammonium propionate, tetramethylammonium butyrate,tetramethylammonium benzoate, tetraethylammonium formate,tetraethylammonium acetate, tetraethylammonium propionate,tetraethylammonium butyrate, tetraethylammonium benzoate,tetrapropylammonium formate, tetrapropylammonium acetate,tetrapropylammonium propionate, tetrapropylammonium butyrate,tetrapropylammonium benzoate, tetrabutylammonium formate,tetrabutylammonium acetate, tetrabutylammonium propionate,tetrabutylammonium butyrate and tetrabutylammonium benzoate andtetrabutylphosphonium acetate, tetrabutylphosphonium formate andethyltriphenylphosphonium acetate, tetrabutylphosphoniumbenzotriazolate, tetraphenylphosphonium phenolate andtrihexyltetradecylphosphonium decanoate, methyltributylammoniumhydroxide, methyltriethylammonium hydroxide, tetramethylammoniumhydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide,tetrabutylammonium hydroxide, tetrapentylammonium hydroxide,tetrahexylammonium hydroxide, tetraoctylammonium hydroxide,tetradecylammonium hydroxide, tetradecyltrihexylammonium hydroxide,tetraoctadecylammonium hydroxide, benzyltrimethylammonium hydroxide,benzyltriethylammonium hydroxide, trimethylphenylammonium hydroxide,triethylmethylammonium hydroxide, trimethylvinylammonium hydroxide,methyltributylammonium methanolate, methyltriethylammonium methanolate,tetramethylammonium methanolate, tetraethylammonium methanolate,tetrapropylammonium methanolate, tetrabutylammonium methanolate,tetrapentylammonium methanolate, tetrahexylammonium methanolate,tetraoctylammonium methanolate, tetradecylammonium methanolate,tetradecyltrihexylammonium methanolate, tetraoctadecylammoniummethanolate, benzyltrimethylammonium methanolate, benzyltriethylammoniummethanolate, trimethylphenylammonium methanolate, triethylmethylammoniummethanolate, trimethylvinylammonium methanolate, methyltributylammoniumethanolate, methyltriethylammonium ethanolate, tetramethylammoniumethanolate, tetraethylammonium ethanolate, tetrapropylammoniumethanolate, tetrabutylammonium ethanolate, tetrapentylammoniumethanolate, tetrahexylammonium ethanolate, tetraoctylammoniummethanolate, tetradecylammonium ethanolate, tetradecyltrihexylammoniumethanolate, tetraoctadecylammonium ethanolate, benzyltrimethylammoniumethanolate, benzyltriethylammonium ethanolate, trimethylphenylammoniumethanolate, triethylmethylammonium ethanolate, trimethylvinylammoniumethanolate, methyltributylammonium benzylate, methyltriethylammoniumbenzylate, tetramethylammonium benzylate, tetraethylammonium benzylate,tetrapropylammonium benzylate, tetrabutylammonium benzylate,tetrapentylammonium benzylate, tetrahexylammonium benzylate,tetraoctylammonium benzylate, tetradecylammonium benzylate,tetradecyltrihexylammonium benzylate, tetraoctadecylammonium benzylate,benzyltrimethylammonium benzylate, benzyltriethylammonium benzylate,trimethylphenylammonium benzylate, triethylmethylammonium benzylate,trimethylvinylammonium benzylate, tetramethylammonium fluoride,tetraethylammonium fluoride, tetrabutylammonium fluoride,tetraoctylammonium fluoride, benzyltrimethylammonium fluoride,tetrabutylphosphonium hydroxide, tetrabutylphosphonium fluoride,tetrabutylammonium chloride, tetrabutylammonium bromide,tetrabutylammonium iodide, tetraethylammonium chloride,tetraethylammonium bromide, tetraethylammonium iodide,tetramethylammonium chloride, tetramethylammonium bromide,tetramethylammonium iodide, benzyltrimethylammonium chloride,benzyltriethylammonium chloride, benzyltripropylammonium chloride,benzyltributylammonium chloride, methyltributylammonium chloride,methyltripropylammonium chloride, methyltriethylammonium chloride,methyltriphenylammonium chloride, phenyltrimethylammonium chloride,benzyltrimethylammonium bromide, benzyltriethylammonium bromide,benzyltripropylammonium bromide, benzyltributylammonium bromide,methyltributylammonium bromide, methyltripropylammonium bromide,methyltriethylammonium bromide, methyltriphenylammonium bromide,phenyltrimethylammonium bromide, benzyltrimethylammonium iodide,benzyltriethylammonium iodide, benzyltripropylammonium iodide,benzyltributylammonium iodide, methyltributylammonium iodide,methyltripropylammonium iodide, methyltriethylammonium iodide,methyltriphenylammonium iodide and phenyltrimethylammonium iodide,methyltributylammonium hydroxide, methyltriethylammonium hydroxide,tetramethylammonium hydroxide, tetraethylammonium hydroxide,tetrapropylammonium hydroxide, tetrabutylammonium hydroxide,tetrapentylammonium hydroxide, tetrahexylammonium hydroxide,tetraoctylammonium hydroxide, tetradecylammonium hydroxide,tetradecyltrihexylammonium hydroxide, tetraoctadecylammonium hydroxidebenzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide,trimethylphenylammonium hydroxide, triethylmethylammonium hydroxide,trimethylvinylammonium hydroxide, tetramethylammonium fluoride,tetraethylammonium fluoride, tetrabutylammonium fluoride,tetraoctylammonium fluoride and benzyltrimethylammonium fluoride. Thesecatalysts can be added alone or in a mixture. They can also have beenencapsulated or bound to a polymer. It is preferable to usetetraethylammonium benzoate and tetrabutylammonium hydroxide.

The proportion of catalysts C) can be from 0.1 to 5% by weight,preferably from 0.3 to 2% by weight, based on the entire formulation.

Co-catalysts C1) used are epoxides. Examples of compounds used here areglycidyl ethers and glycidyl esters, aliphatic epoxides, diglycidylethers based on bisphenol A and glycidyl methacrylates. Examples ofthese epoxides are triglycidyl isocyanurate (TGIC, trade name ARALDITE810, Huntsman), mixtures of diglycidyl terephthalate and triglycidyltrimellitate (trade name ARALDITE PT 910 and 912, Huntsman), glycidylesters of versatic acid (trade name KARDURA E10, Shell),3,4-epoxy-cyclohexylmethyl 3′,4′-epoxycyclohexanecarboxylate (ECC),diglycidyl ether based on bisphenol A (trade name EPIKOTE 828, Shell)ethylhexyl glycidyl ether, butyl glycidyl ether, pentaerythritoltetraglycidyl ether, (trade name POLYPDX R16, UPPC AG), and also otherPolypox grades having free epoxy groups. It is also possible to usemixtures. Preference is given to use of ARALDITE PT 910 and 912.

Other co-catalysts C2) that can be used are metal acetylacetonates.Examples of these are zinc acetylacetonate, lithium acetylacetonate andtin acetylacetonate, alone or in a mixture. It is preferable to use zincacetylacetonate.

The proportion of co-catalysts C1) and/or C2) can be from 0.1 to 5% byweight, preferably from 0.3 to 2% by weight, based on the entireformulation.

The formulations according to the invention can optionally compriseadhesion promoters D). Adhesion promoters for radiation-curableformulations for metallic substrates are generally composed ofphosphoric acid and/or phosphonic acid and/or their reaction products(e.g. esters) with functionalized acrylates. While the free phosphoricacid groups are responsible for direct adhesion to the metal, theacrylate groups provide a bond to the coating matrix. These products aredescribed by way of example in WO 01/98413, in JP 08231564, and in JP06313127, the disclosure of which is incorporated herein by way ofreference.

Typical commercially available products are EBECRYL 168, 169 and 170from Cytec, ALDITOL Vxl 6219 from VIANOVA, CD 9050 and CD 9052 fromSartomer, SIPOMER PAM-100, SIPOMER PAM-200 and SIPOMER PAM-300 fromRhodia and GENORAD 40 from Rahn.

If D) is present in the formulation, its amount is from 0.1 to 10% byweight, preferably from 1 to 5% by weight, based on the entireformulation.

Photoinitiators E) can likewise be present in the formulations accordingto the invention. Suitable photoinitiators and their preparation aredescribed by way of example in “Radiation Curing in Polymer Science &Technology, Vol II: Photoinitiating Systems” by J. P. Fouassier, J. F.Rabek, Elsevier Applied Science, London and New York, 1993. Thesepreferably involve α-hydroxy ketones or derivatives of the same. If thephotoinitiators are present, their amounts present can be from 0.2 to10% by weight, based on the entire formulation. Suitable photoinitiatorsare obtainable with trade names LUCERIN (BASF), IRGACURE and DAROCUR(Ciba).

Acids, mentioned under F), are any of the substances, solid or liquid,organic or inorganic, monomeric or polymeric, which possess theproperties of a Brönstedt or Lewis acid. Examples that may be mentionedare: sulphuric acid, acetic acid, benzoic acid, malonic aid,terephthalic acid, phthalic acid, and also copolyesters or copolyamideswhose acid number is at least 20.

If these acids F) are present, their amounts can be from 0.1 to 10% byweight, based on the entire formulation.

Among the polymers G) or oligomers containing hydroxy groups preferenceis given to use of polyesters, polyethers, polyacrylates, polyurethanes,polyethers and/or polycarbonates whose OH number is from 20 to 500 (inmg KOH/gram) and whose average molar mass is from 250 to 6000 g/mol.These polymers can be amorphous or semicrystalline. Particularpreference is given to polyesters containing hydroxy groups whose OHnumber is from 20 to 150 and whose average molar mass is from 500 to 6000 g/mol. It is, of course, also possible to use a mixture of thesepolymers. Polyesters are preferably used as polymer G). The carboxylicacids preferred for the preparation of these polyesters can be ofaliphatic, cycloaliphatic, aromatic and/or heterocyclic type and, ifappropriate, can have substitution by halogen atoms, and/orunsaturation. Examples of these that may be mentioned are: succinicacid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalicacid, terephthalic acid, isophthalic acid, trimellitic acid,pyromellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid,hexahydroterephthalic acid, dichlorophthalic acid, tetrachlorophthalicacid, endomethylenetetrahydrophthalic acid, glutaric acid, maleic acidand fumaric acid, and—to the extent that they are obtainable—anhydridesthereof, dimethyl terephthalate, bis(glycol) terephthalate, and moreovercyclic monocarboxylic acids, such as benzoic acid, p-tert-butyl benzoicacid or hexahydrobenzoic acid.

Examples of polyhydric alcohols that can be used to produce thepolyester G) are ethylene glycol, propylene 1,2- and 1,3-glycol,butylene 1,4- and 2,3-glycol, di-β-hydroxyethylbutanediol,1,6-hexanediol, 1,8-octanediol, neopentyl glycol, cyclohexanediol,bis(1,4-hydroxymethyl)propane, 2-methyl-1,3-propanediol,2-methyl-1,5-pentanediol, 2,2,4(2,4,4)-trimethyl-1,6-hexanediol,glycerol, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol,1,2,4-butanetriol, tris(β-hydroxyethyl) isocyanurate, pentaerythritol,mannitol and sorbitol, and also diethylene glycol, triethylene glycol,tetraethylene glycol, dipropylene glycol, polypropylene glycol,polybutylene glycol, xylylene glycol and neopentyl glycolhydroxypivalate.

Other starting materials that can be used to produce the polymers G) aremono- and polyesters composed of lactones, e.g. ε-caprolactone, orhydroxycarboxylic acids, e.g. hydroxypivalic acid, ε-hydroxydecanoicacid, ε-hydroxycapronic acid, thioglycolic acid. Polyesters composed ofthe abovementioned polycarboxylic acids or their derivatives and ofpolyphenols, such as hydroquinone, bisphenol A, 4,4′-dihydroxy-biphenylor bis(4-hydroxyphenyl) sulphone; polyesters of carbonic acid, which areobtainable from hydroquinone, from diphenylolpropane, from p-xylyleneglycol, from ethylene glycol, from butanediol or from 1,6-hexanediol andfrom other polyols via conventional condensation reactions, e.g. usingphosgene or diethyl or diphenyl carbonate, or from cyclic carbonates,such as glycol carbonate or vinylidene carbonate, via polymerization ina known manner; polyesters of silicic acid, polyesters of phosphoricacid, e.g. composed of methane-, ethane-, 3-chloroethane-, benzene- orstyrenephosphoric acid, or their derivates for example phosphorylchlorides or phosphoric esters and from polyalcohols or polyphenols ofthe abovementioned type; polyesters of boric acid; polysiloxanes, e.g.the products obtainable by hydrolysis of dialkyldichlorosilanes withwater and subsequent treatment with polyalcohols, the productsobtainable by an addition reaction of polysiloxane dihydrides ontoolefins, such as allyl alcohol or acrylic acid, are suitable as startingmaterials for production of the polymer G).

Other preferred polyesters G) are the reaction products ofpolycarboxylic acids and glycidic compounds, as described by way ofexample in DE-A 24 10 513.

Examples of glycidyl compounds that can be used are esters of2,3-epoxy-1-propanol with monobasic acids which have from 4 to 18 carbonatoms, e.g. glycidyl palmitate, glycidyl laurate and glycidyl stearate,alkylene oxides having from 4 to 18 carbon atoms, e.g. butylene oxide,and glycidyl ethers, such as octyl glycidyl ether.

The polyesters G) can be obtained in a manner known per se bycondensation in an inert gas atmosphere at temperatures of from 100 to260° C., preferably from 130 to 220° C., in the melt, or by anazeotropic method, as described by way of example in Methoden derOrganischen Chemie [Methods of Organic Chemistry] (Houben-Weyl); Volume14/2, pages 1 to 5, 21 to 23, 40 to 44, Georg Thieme Verlag, Stuttgart,1963, or in C. R. Martens, Alkyd Resins, pages 51 to 59, ReinholdPlastics Appl. Series, Reinhold Publishing Comp., New York, 1961.

Other polymers G) that can be used are hydroxy-functional polyethers andpolycarbonates. Preferred polyethers can by way of example be producedby polyaddition of epoxides, such as ethylene oxide, propylene oxide,butylene oxide, trimethylene oxide,3,3-bis(chloromethyl)oxabicyclobutane, tetrahydrofuran, styrene oxide orthe bis-(2,5)-epoxypropyl ether of diphenyloipropane, by cationicpolymerization in the presence of Lewis acids, e.g. boron trifluoride,or by anionic polymerization using alkali metal hydroxides or alkalimetal alcoholates or by an addition reaction of these epoxides, ifappropriate in a mixture or in succession, onto the starter componentshaving reactive hydrogen atoms, e.g. alcohols and/or amines, and/orwater, in particular ethylene glycol, polypropylene 1,3- or 1,2-glycol,pentamethylene glycol, hexanediol, decamethylene glycol,trimethylolpropane, glycerol, aniline, ammonia, ethanolamine,ethylenediamine, di(β-hydroxy-propyl)methylamine, or elsehydroxyalkylated phenols, e.g. di(β-hydroxy-ethoxy)resorcinol.

Polymers G) mentioned by way of example and having carbonate groups,i.e. polycarbonates, can be obtained in a known manner via reaction ofdihydric or trihydric alcohols of molar mass range from 62 to 300 g/molwith diaryl carbonates, e.g. diphenyl carbonate, phosgene or preferablycyclic carbonates, e.g. trimethylene carbonate or2,2-dimethyltrimethylene carbonate (NPC) or a mixture of these cycliccarbonates. Particularly preferred carbonatediols are those which can beprepared, with ring opening, from NPC and, as starter molecules, thedihydric alcohols mentioned.

Other suitable examples of polymers G) are the compounds known per se inpolyurethane chemistry from the group of polythioethers, polyacetals,polyepoxides, polyesteramides or polyurethanes of molar mass range from250 to 8500 g/mol, these having hydroxy groups reactive towardsisocyanate groups.

It is, of course, also possible to use a mixture of the abovementionedpolymers G).

Suitable monomeric alcohols G) are mono-, di- and/or polyols whose molarmass is at least 32 g/mol.

Examples of the monoalcohols are methanol, ethanol, n-propanol,isopropanol, n-butanol, isobutanol, sec-butanol, the isomeric pentanols,hexanols, octanols and nonanols, n-decanol, n-dodecanol, n-tetradecanol,n-hexadecanol, n-octadecanol, cyclohexanol, the isomericmethylcyclohexanols, and also hydroxymethylcyclohexane.

The diols involved by way of example ethylene glycol, triethyleneglycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol,3-methyl-1,5-pentanediol, neopentyl glycol,2,2,4(2,4,4)-trimethylhexanediol, and also neopentyl glycolhydroxypivalate.

The triols involved by way of example trimethylolpropane,ditrimethylolpropane, trimethylolethane, 1,2,6-hexanetriol,1,2,4-butanetriol, tris(β-hydroxyethyl) isocyanurate, pentaerythritol,mannitol or sorbitol.

If G) is present, its amount, based on the entire formulation, can befrom 0.1 to 40% by weight.

Suitable pigments H) for the radiation-curable formulations according tothe present invention are described by way of example in “RadiationCuring in Polymer Science & Technology, Vol IV: Practical Aspects andApplication” by J. P. Fouassier, J. F. Rabek, Elsevier Applied Science,London and New York, 1993, Chapter 5, pages 87 to 105, and their amountspresent can be from 1 to 40% by weight. Examples of corrosion-preventionpigments are found by way of example in Pigment+Füllstoff Tabellen[Pigment+Filler Tables], O. Lückert, Vincentz Verlag Hannover, 6thEdition 2002. Examples that may be mentioned are: SHIELDEX C 303 (GraceDavison) and HALOX Coil X 100, HALOX Coil X 200 and HALOX CW 491(Erbslöh), HEUCOPHOS SAPP, or else ZPA (Heubach), K-White TC 720 (Tayca)and HOMBICOR (Sachtleben). It is, of course, also possible to use simpleinorganic salts, e.g. zinc phosphate, or else colorant pigments. Ifthese pigments are present, their amount varies from 1 to 50% by weight,based on the entire formulation.

Other additives H) for the radiation-curable formulations are availablein various compositions and for various purposes, e.g. flow controlagents, matting agents, degassing agents, dyes, etc.

Some of these are described in the brochure “SELECTED DEGUSSA PRODUCTSFOR RADIATION CURING AND PRINTING INKS”, published by Tego Coating & InkAdditives, Essen, 2003. If these additives are present, their amountvaries from 0.01 to 5% by weight, based on the entire formulation.

Solvents I) that can be used are any of the organic and inorganicliquids which are inert under the reaction conditions. Examples that maybe mentioned are acetone, ethyl acetate, butyl acetate, xylene, Solvesso100, Solvesso 150, methoxypropyl acetate and dibasic esters and water.

If solvents are present, their amount is from 1 to 70% by weight, basedon the entire formulation.

The homogenization of all of the constituents to produce the compositionof the invention can take place in suitable assemblies, e.g. heatablestirred tanks, kneaders, or else extruders, and the upper temperaturelimits which should not be exceeded here are from 120 to 130° C.

The well-mixed composition is applied to the substrate by a suitableapplication method (e.g. roller coating, spraying, dip-coating). Afterapplication, the coated workpieces are passed for hardening in thepresence of photoinitiators under a UV lamp (with or without inert gas)or in the absence of photoinitiators under an electron-beam curingsystem (EBCS), and then heated for from 4 to 60 minutes to a temperatureof from 60 to 220° C., preferably from 6 to 30 minutes at from 80 to160° C. In principle, the inverse hardening sequence is alsoconceivable.

The same thermal hardening without prior radiation-curing is carried outas comparative experiment.

UV curing and UV lamps are described by way of example in “RadiationCuring in Polymer Science & Technology, Vol I: Fundamentals and Methods”by J. P. Fouassier, J. F. Rabek, Elsevier Applied Science, London andNew York, 1993, Chapter 8, pages 453 to 503.

Electron-beam curing systems and electron-beam hardening systems aredescribed by way of example in “Radiation Curing in Polymer Science &Technology, Vol I: Fundamentals and Methods” by J. P. Fouassier, J. F.Rabek, Elsevier Applied Science, London and New York, 1993, Chapter 4,pages 193 to 225 and in Chapter 9, pages 503 to 555.

The present invention further provides the use of the thermally curableand radiation-curable formulations according to the invention as coatingcompositions, in particular as primer, intermediate layer, topcoatmaterial, clear-coat material or sealing material, and also the coatingcompositions themselves.

The invention also provides the use of the thermally curable andradiation-curable formulations according to the invention for theproduction of liquid and pulverulent coatings on metal substrates, onplastics substrates, on glass substrates, on wood substrates, or onleather substrates, or on other heat-resistant substrates.

The invention also provides the use of the thermally curable andradiation-curable formulations according to the invention as adhesivecompositions for adhesive bonding of metal substrates, of plasticssubstrates, of glass substrates, of wood substrates, of textilesubstrates, or of leather substrates, or of other heat-resistantsubstrates.

The invention likewise provides metal-coating compositions, inparticular for automobile bodywork, for motorcycles and peddle cycles,for parts of buildings and for household devices, wood-coatingcompositions, glass-coating compositions, textile-coating compositions,leather-coating compositions and plastics-coating compositions.

The coating can either be used alone or can be one layer of a multilayerstructure. It can by way of example be applied in the form of primer, inthe form of intermediate layer, or in the form of topcoat material orclear-coat material. The layers situated over or under the coating canbe hardened either by a conventional thermal method or else byradiation.

The present invention is further illustrated below, using examples.Alternative embodiments of the present invention are obtainable by ananalogous method.

EXAMPLES

Starting materials Product description, producer IPDI Isophoronediisocyanate, Evonik Degussa GmbH, Coatings & Colorants IPDI uretdioneIPDI-based uretdione, Evonik Degussa GmbH, Coatings & Colorants, freeNCO content 17.2%, total NCO 36% Dynapol R 110 radiation-curable resin(urethane acrylate) in 25% of isobornyl acrylate, Evonik Degussa GmbH,Coatings & Colorants (A) VESTAGON EP BF Hardening agent, uretdionecontent: from 11.5 to 13.0%, 9030 melting point: from 74 to 75° C.,T_(G): from 40 to 50° C., Evonik Degussa GmbH, Coatings & Colorants (B)HEA Hydroxyethyl acrylate, Evonik Degussa GmbH LAROMER 8887Trimethylolpropane monoformal acrylate, BASF, monofunctional reactivediluent (A) IRGACURE 184 Photoinitiator, Ciba (E) ARALDITE PT 912Co-catalyst, glycidyl ester, Huntsman (C1) Zinc acetylacetonateCo-catalyst, Aldrich (C2) TEAB Tetraethylammonium benzoate, RSA Corp.(C) DBTL Dibutyltin dilaurate, catalyst, Aldrich

A) Production of Radiation-Curable Resin A1) Polyester Production

Adipic acid (292 g) and butanediol (295 g) are melted in a stream ofnitrogen, in a 2 l flask with distillation head. When a temperature of160° C. is reached, water begins to distil over. Within a period of onehour, the temperature is successively increased to 220° C. After fourfurther hours at this temperature, water elimination becomes slower. 200mg of FASCAT 4102 (transesterification catalyst from Arkema) areincorporated by stirring and the process is continued under a vacuumwhich during the course of the reaction is adjusted in such a way thatproduction of distillate always continues. The process ends after ahydroxy number of 250 mg KOH/g (DIN 53240-2 method) and an acid numberof 0.6 mg KOH/g (DIN EN ISO 2114 method) has been reached. Viscosity(80° C.): 41 mPas.

A2) Acrylation of A1

139 g of HEA and 224 g of the polyester A1 were added to 222 g of IPDI.After addition of 0.7 g of IONOL CP and 0.1 g of DBTL, the mixture isheated to 60° C., with stirring, and then stirred at this temperaturefor 5 h. After this, the NCO number has fallen to <01%.

B) Preparation of Uretdione-Containing Component

408 g of IPDI uretdione (free NCO number 17.2%) is dissolved in 500 mlof ethyl acetate; 72 g of hexanediol and 71 g of HEA are admixed. Afteraddition of 0.3 g of Ionol CP and 0.1 g of DBTL, the mixture is heatedto 60° C., and cooled after 5 h. Free NCO content has fallen to <0.1%.The solvent is drawn off on a rotary evaporator, and the product is awhite crystalline solid.

C) Formulations

All data in % by weight are based on the total weight of the formulation

Experiment/component 1 2* 3 4* 5 Dynapol R 110 (A) 32 33 32 VESTAGON BF9030 (B) 33 33 33 Radiation-curable resin (A) 30 30 LAROMER 8887 (A) 4042 33 34 33 Uretdione component (B) 20 20 IRGACURE 184 (E) 8  8 — TEAB(C) 1 —  1 1 Zinc acetylacetonate (C2) 1 ARALDITE PT 912 (C1) 1 —  1*comparative examples not according to the invention

D) Results General Production Specification for the Formulation andHardening of UV Coatings

All of the constituents of the formulation were combined and stirred bya magnetic stirrer for 20 min.

The ready-to-use formulation is applied by doctor blade at a layerthickness of from 20 to 25 μm to a steel sheet (Bonder 1303 sheet) andthen in case 1 and 2* hardened under a UV lamp (3 m/min, Minicure,mercury vapour lamp, 80 W/cm, Technigraf). In cases 3 and 4, thehardening takes place under electron beams (EBCS, 10 Mrad, equipmentfrom ESI), since no photoinitiators are present. Thermal curing in aconvection oven at 150° C. (30 min) follows this in all cases. In caseb), thermal hardening takes place without prior radiation curing.

1a) UV + 30 min 1b) 30 min Experiment 1 150° C. 150° C. Erichsenindentation [mm] 8.5 9.0 Ball impact (dir./rev.) >80/>80 60/40 [inch ×lbs] MEK test [cycles] >100 38 Freedom from tack yes yes

2a) UV + 30 min 2b) 30 min Experiment 2* 150° C. 150° C. Erichsenindentation [mm] 9.0 9.0 Ball impact (dir./rev.) 30/<10 20/<10 [inch ×lbs] MEK test [cycles] 57 2 Freedom from tack yes no *comparativeexamples not according to the invention

3a) EBCS + 30 min 3b) 30 min Experiment 3 150° C. 150° C. Erichsenindentation 9.5 10.0 [mm] Ball impact (dir./rev.) >80/>80 >80/>80 [inch× lbs] MEK test [cycles] >100 23 Freedom from tack yes yes

4a) UV + 30 min 4b) 30 min Experiment 4* 150° C. 150° C. Erichsenindentation 10.0 9.0 [mm] Ball impact (dir./rev.) 50/<10 50/<10 [inch ×lbs] MEK test [cycles] 70 1 Freedom from tack yes no *comparativeexamples not according to the invention

5a) EBCS + 30 5b) 30 min Experiment 5 min 150° C. 150° C. Erichsenindentation 10.0 10.0 [mm] Ball impact (dir./rev.) >80/>80 >80/>80 [inch× lbs] MEK test [cycles] >100 34 Freedom from tack yes yes

Erichsen Indentation to DIN 53156, Ball Impact to ASTM D2794-93

The formulations according to the invention are superior in all of thecoatings data to the formulations not according to the invention. Moreparticularly, the formulation according to the invention exhibits aminimum extent of coating properties after thermal curing even withoutprior radiation curing: freedom from tack, flexibility (Erichsenindentation >7 mm) and chemicals resistance (MEK test >20 cycles).

1. A thermally curable and radiation-curable formulation comprising A)from 5 to 90% by weight of at least one radiation-curable component,which optionally comprises OH groups, B) from 10 to 90% by weight of atleast one component comprising uretdione groups, which optionallycomprises at least one of OH groups and radiation-curable groups, C)from 0.1 to 5% by weight of at least one of tetralkylammonium salt andphosphonium salt with at least one of halogens, hydroxides, alcoholatesand organic or inorganic acid anions, as counter-ion, and from 0.1 to 5%by weight of at least one co-catalyst, selected from the groupconsisting of C1) at least one epoxide and C2) at least one metalacetylacetonate.
 2. The thermally curable and radiation-curableformulation according to claim 1, wherein the formulation furthercomprises at least one of following components, alone or in a mixture:D) from 0.1 to 10% by weight of at least one adhesion promoter, E) from0.2 to 10% by weight of at least one photoinitiator, F) from 0.1 to 10%by weight of at least one acid, G) from 1 to 40% by weight of at leastone of monomers, polymers and oligomers comprising hydroxy groups, H)from 0.01 to 50% by weight of at least one of pigment and otheradditives, I) from 1 to 70% by weight of at least one solvent.
 3. Thethermally curable and radiation-curable formulation according to claim1, wherein the component A) present comprises at least one of epoxyacrylates, polyester acrylates, polyether acrylates, polyacrylateacrylate, urethane acrylates and polyester urethane acrylates, alone orin a mixture.
 4. The thermally curable and radiation-curable formulationaccording to claim 1, wherein the component A) present comprises apolyester urethane acrylate.
 5. The thermally curable andradiation-curable formulation according to claim 1, wherein thecomponent A) present comprises a reactive diluent.
 6. The thermallycurable and radiation-curable formulation according to claim 5, whereinthe formulation comprises isobornyl acrylate, hydroxypropylmethacrylate, trimethylolpropane monoformal acrylate, tetrahydrofurfurylacrylate, phenoxyethyl acrylate, trimethylenepropane triacrylate,dipropylene glycol diacrylate, tripropylene glycol diacrylate,hexanediol diacrylate, pentaerythritol tetraacrylate, lauryl acrylate,or else propoxylated or ethoxylated variants of these reactive diluentsand/or urethanized reactive diluents, vinyl ether or allyl ether.
 7. Thethermally curable and radiation-curable formulation according to claim6, wherein the formulation comprises at least one of isobornyl acrylateand trimethylolpropane monoformal acrylate.
 8. The thermally curable andradiation-curable formulation according to claim 1, wherein component B)comprises an uretdione group and based on isophorone diisocyanate(IPDI), at least one of hexamethylene diisocyanate (HDI),dicyclohexylmethane 2,2′-diisocyanate/dicyclohexylmethane2,4′-diisocyanate/dicyclohexylmethane 4,4′-diisocyanate (H₁₂MDI),2-methyl pentadiisocyanate (MPDI), trimethylhexamethylene2,2,4-diisocyanate/trimethylhexamethylene 2,4,4-diisocyanate (TMDI),norbornane diisocyanate (NBDI), methylenediphenyl diisocyanate (MDI),toluidine diisocyanate (TDI) and tetramethylxylylene diisocyanate(TMXDI), alone or in a mixture.
 9. The thermally curable andradiation-curable formulation according to claim 8, characterized inthat component B) comprises an uretdione group and based on IPDI, atleast one of 4,4′-H₁₂MDI and HDI are present.
 10. The thermally curableand radiation-curable formulation according to claim 1, component B) hasan uretdione group and, based on, alone or in a mixture, at least one ofmonoalcohols, monoamines, tetra-, tri-, and dialcohols of low molecularweight, polyurethanes, polyesteramides, polyepoxides, polycaprolactones,polyethers, polythioethers, and polyesters comprising hydroxy groups.11. The thermally curable and radiation-curable formulation according toclaim 10, wherein the formulation comprises at least one of polyestersand monomeric dialcohols.
 12. The thermally curable andradiation-curable formulation according to claim 1, wherein thecomponent B) comprising an uretdione group has less than 5% by weight offree NCO content and from 6 to 25% by weight content of uretdione groups(calculated as C₂N₂O₂, molecular weight 84).
 13. The thermally curableand radiation-curable formulation according to claim 1, wherein thecomponent B) comprising an uretdione groups also has at least one ofisocyanurate structures, biuret structures, allophanate structures,urethane structures and urea structures.
 14. The thermally curable andradiation-curable formulation according to claim 1, wherein thecomponent C) present comprises at least one of tetramethylammoniumformate, tetramethylammonium acetate, tetramethylammonium propionate,tetramethylammonium butyrate, tetramethylammonium benzoate,tetraethylammonium formate, tetraethylammonium acetate,tetraethylammonium propionate, tetraethylammonium butyrate,tetraethylammonium benzoate, tetrapropylammonium formate,tetrapropylammonium acetate, tetrapropylammonium propionate,tetrapropylammonium butyrate, tetrapropylammonium benzoate,tetrabutylammonium formate, tetrabutylammonium acetate,tetrabutylammonium propionate, tetrabutylammonium butyrate andtetrabutylammonium benzoate and tetrabutylphosphonium acetate,tetrabutylphosphonium formate and ethyltriphenylphosphonium acetate,tetrabutylphosphonium benzotriazolate, tetraphenylphosphonium phenolateand trihexyltetradecylphosphonium decanoate, methyltributylammoniumhydroxide, methyltriethylammonium hydroxide, tetramethylammoniumhydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide,tetrabutylammonium hydroxide, tetrapentylammonium hydroxide,tetrahexylammonium hydroxide, tetraoctylammonium hydroxide,tetradecylammonium hydroxide, tetradecyltrihexylammonium hydroxide,tetraoctadecylammonium hydroxide, benzyltrimethylammonium hydroxide,benzyltriethylammonium hydroxide, trimethylphenylammonium hydroxide,triethylmethylammonium hydroxide, trimethylvinylammonium hydroxide,methyltributylammonium methanolate, methyltriethylammonium methanolate,tetramethylammonium methanolate, tetraethylammonium methanolate,tetrapropylammonium methanolate, tetrabutylammonium methanolate,tetrapentylammonium methanolate, tetrahexylammonium methanolate,tetraoctylammonium methanolate, tetradecylammonium methanolate,tetradecyltrihexylammonium methanolate, tetraoctadecylammoniummethanolate, benzyltrimethylammonium methanolate, benzyltriethylammoniummethanolate, trimethylphenylammonium methanolate, triethylmethylammoniummethanolate, trimethylvinylammonium methanolate, methyltributylammoniumethanolate, methyltriethylammonium ethanolate, tetramethylammoniumethanolate, tetraethylammonium ethanolate, tetrapropylammoniumethanolate, tetrabutylammonium ethanolate, tetrapentylammoniumethanolate, tetrahexylammonium ethanolate, tetraoctylammoniummethanolate, tetradecylammonium ethanolate, tetradecyltrihexylammoniumethanolate, tetraoctadecylammonium ethanolate, benzyltrimethylammoniumethanolate, benzyltriethylammonium ethanolate, trimethylphenylammoniumethanolate, triethylmethylammonium ethanolate, trimethylvinylammoniumethanolate, methyltributylammonium benzylate, methyltriethylammoniumbenzylate, tetramethylammonium benzylate, tetraethylammonium benzylate,tetrapropylammonium benzylate, tetrabutylammonium benzylate,tetrapentylammonium benzylate, tetrahexylammonium benzylate,tetraoctylammonium benzylate, tetradecylammonium benzylate,tetradecyltrihexylammonium benzylate, tetraoctadecylammonium benzylate,benzyltrimethylammonium benzylate, benzyltriethylammonium benzylate,trimethylphenylammonium benzylate, triethylmethylammonium benzylate,trimethylvinylammonium benzylate, tetramethylammonium fluoride,tetraethylammonium fluoride, tetrabutylammonium fluoride,tetraoctylammonium fluoride, benzyltrimethylammonium fluoride,tetrabutylphosphonium hydroxide, tetrabutylphosphonium fluoride,tetrabutylammonium chloride, tetrabutylammonium bromide,tetrabutylammonium iodide, tetraethylammonium chloride,tetraethylammonium bromide, tetraethylammonium iodide,tetramethylammonium chloride, tetramethylammonium bromide,tetramethylammonium iodide, benzyltrimethylammonium chloride,benzyltriethylammonium chloride, benzyltripropylammonium chloride,benzyltributylammonium chloride, methyltributylammonium chloride,methyltripropylammonium chloride, methyltriethylammonium chloride,methyltriphenylammonium chloride, phenyltrimethylammonium chloride,benzyltrimethylammonium bromide, benzyltriethylammonium bromide,benzyltripropylammonium bromide, benzyltributylammonium bromide,methyltributylammonium bromide, methyltripropylammonium bromide,methyltriethylammonium bromide, methyltriphenylammonium bromide,phenyltrimethylammonium bromide, benzyltrimethylammonium iodide,benzyltriethylammonium iodide, benzyltripropylammonium iodide,benzyltributylammonium iodide, methyltributylammonium iodide,methyltripropylammonium iodide, methyltriethylammonium iodide,methyltriphenylammonium iodide and phenyltrimethylammonium iodide,methyltributylammonium hydroxide, methyltriethylammonium hydroxide,tetramethylammonium hydroxide, tetraethylammonium hydroxide,tetrapropylammonium hydroxide, tetrabutylammonium hydroxide,tetrapentylammonium hydroxide, tetrahexylammonium hydroxide,tetraoctylammonium hydroxide, tetradecylammonium hydroxide,tetradecyltrihexylammonium hydroxide, tetraoctadecylammonium hydroxidebenzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide,trimethylphenylammonium hydroxide, triethylmethylammonium hydroxide,trimethylvinylammonium hydroxide, tetramethylammonium fluoride,tetraethylammonium fluoride, tetrabutylammonium fluoride,tetraoctylammonium fluoride and benzyltrimethylammonium fluoride, aloneor in a mixture.
 15. The thermally curable and radiation-curableformulation according to claim 14, wherein the component C) presentcomprises tetraethylammonium benzoate or tetrabutylammonium hydroxide.16. The thermally curable and radiation-curable formulation according toclaim 1, wherein the component C1) present comprises at least one ofglycidyl ethers, glycidyl esters, aliphatic epoxides, diglycidyl etherscomprising bisphenol A and glycidyl methacrylates.
 17. The thermallycurable and radiation-curable formulation according to claim 16, whereinthe formulation comprises at least one of triglycidyl isocyanurate, amixture comprising diglycidyl terephthalate and triglycidyltrimellitate, glycidyl ester of Versatic acid, 3,4-epoxycyclohexylmethyl3′,4′-epoxycyclohexanecarboxylate (ECC), diglycidyl ether based onbisphenol A, ethylhexyl glycidyl ether, butyl glycidyl ether,pentaerythritol tetraglycidyl ether, or other Polypox grades having freeepoxy groups, alone or in a mixture thereof.
 18. The thermally curableand radiation-curable formulation according to claim 1, wherein thecomponent C2) present comprises at least one of zinc acetylacetonate,lithium acetylacetonate and tin acetylacetonate, alone or in a mixture.19. The thermally curable and radiation-curable formulation according toclaim 1, wherein the component D) present comprises at least one ofphosphoric acid, phosphonic acid, and reaction products thereof withfunctionalized acrylates.
 20. The thermally curable andradiation-curable formulation according to claim 1, wherein thecomponent F) present comprises at least one of sulphuric acid, aceticacid, benzoic acid, malonic acid, terephthalic acid, phthalic acid,copolyesters and copolyamides whose acid number is at least
 20. 21. Thethermally curable and radiation-curable formulation according to claim1, wherein the component G) present comprises at least one ofpolyesters, polyethers, polyacrylates, polyurethanes, polyethers andpolycarbonates whose OH number is from 20 to 500 (in mg KOH/gram) andwhose average molar mass is from 250 to 6000 g/mol.
 22. The thermallycurable and radiation-curable formulation according to claim 1, whereinthe component G) present comprises polyesters which comprise hydroxygroups and whose OH number is from 20 to 150 and whose average molarmass is from 500 to 6000 g/mol.
 23. The thermally curable andradiation-curable formulation according to claim 1, wherein thecomponent G) present comprises a reaction product of polycarboxylic acidand glycidic compound.
 24. The thermally curable and radiation-curableformulation according to claim 1, wherein the component G) presentcomprises at least one of polythioethers, polyacetals, polyepoxides,polyesteramides and polyurethanes of molar mass range from 250 to 8500g/mol, which have hydroxy groups reactive towards isocyanate groups. 25.The thermally curable and radiation-curable formulation according toclaim 1, wherein the component G) present comprises at least one ofmono-, di-, and polyols whose molar mass is at least 32 g/mol.
 26. Aprocess for production of thermally curable and radiation-curableformulations according to claim 1, wherein the formulation comprises A)from 5 to 90% by weight of at least one radiation-curable component,which optionally comprises OH groups, B) from 10 to 90% by weight of atleast one component comprising uretdione groups, which optionallycomprises at least one of OH groups and radiation-curable groups, C)from 0.1 to 5% by weight of at least one of tetralkylammonium salt andphosphonium salt with halogens, hydroxides, alcoholates or organic orinorganic acid anions, as counter-ion, and from 0.1 to 5% by weight ofat least one co-catalyst, selected from the group consisting of C1) atleast one epoxide and optionally C2) at least one metal acetylacetonate,and wherein the process comprises homogenizing the formulation at anupper temperature limit of from 120 to 130° C.
 27. A coatingcomposition, comprising the thermally curable and radiation-curableformulation according to claim 1, comprising A) from 5 to 90% by weightof at least one radiation-curable component, which optionally comprisesOH groups, B) from 10 to 90% by weight of at least one componentcomprising uretdione groups, which optionally comprises OH groups and/orradiation-curable groups, C) from 0.1 to 5% by weight of at least one oftetralkylammonium salt and phosphonium salt with halogens, hydroxides,alcoholates or organic or inorganic acid anions, as counter-ion, andfrom 0.1 to 5% by weight of at least one co-catalyst, selected from thegroup consisting of C1) at least one epoxide and optionally C2) at leastone metal acetylacetonate.
 28. A sealing material comprising thecomposition according to claim
 27. 29. A heat-resistant substratecomprising the composition according to claim
 27. 30. A coatingcomposition comprising thermally curable and radiation-curableformulations according to claim 1, comprising A) from 5 to 90% by weightof at least one radiation-curable component, which optionally comprisesOH groups, B) from 10 to 90% by weight of at least one componentcontaining uretdione groups, which can also contain OH groups and/orradiation-curable groups, C) from 0.1 to 5% by weight of at least onetetralkylammonium salt and/or phosphonium salt with halogens,hydroxides, alcoholates or organic or inorganic acid anions, ascounter-ion, and from 0.1 to 5% by weight of at least one co-catalyst,selected from the group consisting of C1) at least one epoxide and C2)at least one metal acetylacetonate.
 31. A metal-coating composition,comprising a thermally curable and radiation-curable formulationcomprising A) from 5 to 90% by weight of at least one radiation-curablecomponent, which optionally comprises OH groups, B) from 10 to 90% byweight of at least one component comprising uretdione groups, whichoptionally comprises OH groups and/or radiation-curable groups, C) from0.1 to 5% by weight of at least one of tetralkylammonium salt andphosphonium salt with halogens, hydroxides, alcoholates or organic orinorganic acid anions, as counter-ion, and from 0.1 to 5% by weight ofat least one co-catalyst, selected from the group consisting of C1) atleast one epoxide and optionally C2) at least one metal acetylacetonate.32. A wood-coating composition, comprising a thermally curable andradiation-curable formulations comprising A) from 5 to 90% by weight ofat least one radiation-curable component, which optionally comprises OHgroups, B) from 10 to 90% by weight of at least one component containinguretdione groups, which optionally comprises OH groups and/orradiation-curable groups, C) from 0.1 to 5% by weight of at least one oftetralkylammonium salt and phosphonium salt with halogens, hydroxides,alcoholates or organic or inorganic acid anions, as counter-ion, andfrom 0.1 to 5% by weight of at least one co-catalyst, selected from thegroup consisting of C1) at least one epoxide and optionally C2) at leastone metal acetylacetonate.
 33. A leather-coating composition ortextile-coating composition, comprising a thermally curable andradiation-curable formulation comprising A) from 5 to 90% by weight ofat least one radiation-curable component, which optionally comprises OHgroups, B) from 10 to 90% by weight of at least one component comprisinguretdione groups, which optionally comprises OH groups and/orradiation-curable groups, C) from 0.1 to 5% by weight of at least one oftetralkylammonium salt and phosphonium salt with halogens, hydroxides,alcoholates or organic or inorganic acid anions, as counter-ion, andfrom 0.1 to 5% by weight of at least one co-catalyst, selected from thegroup consisting of C1) at least one epoxide and optionally C2) at leastone metal acetylacetonate.
 34. A plastic-coating composition orglass-coating composition, comprising a thermally curable andradiation-curable formulation comprising A) from 5 to 90% by weight ofat least one radiation-curable component, which optionally comprises OHgroups, B) from 10 to 90% by weight of at least one component containinguretdione groups, which optionally comprises at least one of OH groupsand radiation-curable groups, C) from 0.1 to 5% by weight of at leastone tetralkylammonium of salt and phosphonium salt with halogens,hydroxides, alcoholates or organic or inorganic acid anions, ascounter-ion, and from 0.1 to 5% by weight of at least one co-catalyst,selected from C1) at least one epoxide and optionally C2) at least onemetal acetylacetonate.
 35. An automobile bodywork comprising themetal-coating composition according to claim
 31. 36. A coatingcomposition comprising the formulation according to claim
 2. 37. Ametal-coating composition comprising the formulation according to claim3.